U.S. patent number 3,719,541 [Application Number 05/017,643] was granted by the patent office on 1973-03-06 for process for the production of precoated metal.
This patent grant is currently assigned to Toray Industries, Inc.. Invention is credited to Shuji Fujioka, Takamitsu Ino, Jiro Mibae, Masao Takahashi, Ryuhei Takigawa.
United States Patent |
3,719,541 |
Takahashi , et al. |
March 6, 1973 |
PROCESS FOR THE PRODUCTION OF PRECOATED METAL
Abstract
Process for the production of a precoated metal which comprises
laminating a film resin layer on the surface of a metal material
through an intermediate layer comprising a radical curable resin
and achieving unification of said laminated product by irradiating
said laminated product from above with an electron beam having an
energy capable of being transmitted to the surface of the metal
material.
Inventors: |
Takahashi; Masao (Ohtsu,
JA), Mibae; Jiro (Ohtsu, JA), Ino;
Takamitsu (Ohtsu, JA), Takigawa; Ryuhei (Ohtsu,
JA), Fujioka; Shuji (Ohtsu, JA) |
Assignee: |
Toray Industries, Inc. (Tokyo,
JA)
|
Family
ID: |
11960168 |
Appl.
No.: |
05/017,643 |
Filed: |
March 9, 1970 |
Foreign Application Priority Data
|
|
|
|
|
Mar 11, 1969 [JA] |
|
|
44/18027 |
|
Current U.S.
Class: |
156/275.5;
156/275.7; 428/461; 428/480; 428/913; 522/81; 522/107; 522/120;
522/149 |
Current CPC
Class: |
B05D
3/068 (20130101); B32B 15/08 (20130101); B29C
63/48 (20130101); Y10T 428/31692 (20150401); Y10S
428/913 (20130101); Y10T 428/31786 (20150401) |
Current International
Class: |
B29C
63/48 (20060101); B32B 15/08 (20060101); B29C
63/00 (20060101); B05D 3/06 (20060101); B01j
001/10 () |
Field of
Search: |
;156/272
;204/159.15,159.14 ;161/188,216,252 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Lehmann; E. E.
Claims
We claim:
1. A process for the production of a precoated metal which
comprises coating the surface of a metal plate with a radical
curable composition, placing a film composed of a synthetic resin
in intimate contact with said radical curable layer and thereafter
irradiating said laminated product with an electron beam having an
energy of 0.1 to 3 MeV in a dose of 0.1 to 20 Mrad, said radical
curable composition comprising a mixture of 30 to 100 percent by
weight of at least one unsaturated polymer including 0.1 to 5
equivalents of carbon-carbon double bonds per 1,000 of the
molecular weight of said unsaturated polymer and 70 to 0 percent by
weight of a vinyl monomer.
2. The process of claim 1 wherein said unsaturated polymer of said
radical curable composition is selected from the group consisting
of vinyl polymers, polyesters, polyester ethers, melamine polymers
and polyamides, and said radical curable composition has a monomer
constituent in common with said synthetic resin.
Description
This invention relates to a pronoucedly improved process for the
production of a precoated metal possessing excellent
properties.
In recent years the production of the precoated metals tends to be
increased to a great degree. This is because the precoated metal as
a material coated or covered at a stage prior to processing renders
capable of a substantially rationalized process for the manufacture
of metal wares as compared with the conventional process of coating
after processing such as press work. The precoated metals
concurrently have an effectiveness for preventing from tarnishing
the metal plate in storage and during the time of
transportation.
For such a process for the manufacture of the precoated metal it is
a most customary method that a paint is coated on the surface
treated metal plate by some suitable means, followed by heating at
elevated temperatures and drying whereby during it.
There are other methods available such that a thin film is caused
to be adhered to at the elevated temperatures or adhered in layers
through an adhesive agent layer.
Since the precoated metals are mainly used outside the house
including roofing materials and side panels of the house,
weather-proof characteristics and anti-corrosive property are
required of the precoated metals. To meet this situation the
so-called two coats has been recently developed, i.e., the
precoated metal is coated twice with paints with a view of causing
the undercoating to contribute for giving an intimate adhesive
property with respect of the metal and anti-corrosive property and
the top coating for giving processability and weather-proof
property. However, satisfactory results have not as yet been
achieved.
An object of the present invention is to provide a novel process
for the production of a new precoated metal capable of having
excellent characteristics over the precoated metals available on
the market concerning various properties (weather-proofness,
anti-corrosiveness, processability, etc.) necessary for a precoated
metal, the said process is substantially rationalized as compared
with the hitherto process of the manufacture.
Other objects of the present invention will be evident from the
below-mentioned description.
It has been found out that these objects of the present invention
can be achieved by laminating in layers a film resin layer on the
surface of a metal material through an intermediate layer
comprising a radical curable resin, the said laminated material
being irradiated from above it by the electron beam having an
energy for transmitting onto the surface of the metal material.
In the present invention, for metal materials consisting of a
substrative material there are used various types of iron sheets
(for example, untreated bare sheet steel, zinc steel sheet, zinc
phosphate treated sheet steel, metal plates in the form of a thin
sheet such as aluminium sheet, copper sheet and metal materials in
a variety of forms such as a rod, wire and mass.
Flat surface is a surface, widely used for forming a laminated
construction and other various forms including curved surface and
wavy shaped surface may also be used. Further, it is possible to
cause a resin layer andpaint film layer to exist on the surfaces of
these metal materials within the range of the objects of the
present invention. This is a thin paint film known as service coat,
anti-rust paint, etc. and is considered en bloc with respect of the
metal material.
For materials forming the intermediate layer, i.e., radical curable
resins, there are named (1) a vinyl polymer containing unsaturated
groups at its side chains, (2) an unsaturated polyester prepared by
using as one of starting materials an unsaturated monocarboxylic
acid or unsaturated dicarboxylic acid, (3) an unsaturated polyester
ether (an epoxy ester) prepared by the condensation of an
unsaturated carboxylic acid and an epoxy resin, (4) a melamine
polymer containing an unsaturated group (for example, a
condensation product of hydroxy alkyl methacrylic acid ester and
melamine), (5) an unsaturated polyamide prepared by using as one of
starting materials an unsaturated monocarboxylic acid or
unsaturated dicarboxylic acid and (6) a mixture of each of the said
unsaturated polymers and vinyl monomers. The amount of the
unsaturated groups contained in these unsaturated polymers varies
in a considerably wide range depending upon the properties required
of the precoated metal. However, in general, favorable results are
obtained in the case of 0.1 to 5, especailly 0.2 to 1.5, mole
equivalent per 1,000 of the molecular weight of a polymer. The
preferred blend ratio of the unsaturated polymer and the vinyl
monomer is 30-100 by weight percent to 70-0 by weight percent.
A mixture of vinyl monomers and a polyurethane prepared by using as
a starting material an acid, alcohol, polyether or polyester
containing an unsaturated groups can also be used in this invention
as a radical curable resin forming the intermediate layer.
Moreover, in this invention, a mixture of a saturated polymer and
unsaturated monomers such for example as a mixture, say, the
so-called acrylic sirup, of a methyl methacrylate polymer and
methyl methacrylate monomer can be used as the radical curable
resin.
For vinyl monomers to be used in the present invention there are
named acrylic acid; acrylates such as methyl acrylate, ethyl
acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate and
hydroxyethyl acrylate; methacrylic acid; methacrylates such as
methyl methacrylate, ethyl methacrylate, butyl methacrylate and
hydroxyethyl methacrylate; acrylic amide; acrylic amide derivatives
such as N,N-dimethyl acrylic amide, N-n-butoxycarbonyl acrylic
amide; methacrylic amide; methacrylic amide derivatives such as
methacrylic amide, N,N-dimethyl methacrylic amide, N-o-anisyl
methacrylic amide; vinyl esters such as vinyl acetate,
vinyl-p-chlorobenzoate, and vinyl pelargonate; itaconic acid;
itaconic acid esters such as diethyl itaconate; maleic acid; maleic
acid esters such as diethyl malate; allyl esters such as allyl
stearate and methallyl laurate; vinyl ketones such as
methyl-.alpha.-methyl vinyl ketone; vinyl ethers such as n-hexyl
vinyl ether, stearyl vinyl ether; styrene; styrene deviratives such
as p-chlorostyrene, .alpha.-methyl styrene; olefine derivatives
such as 3-methyl-vinyl cyclohexane and 4-phenyl-1-butene;
halogenated ethylene such as 1-chloro-1,2-dibromo-ethylene;
acrylonitrile; methacrylonitrile; silane derivatives such as allyl
trichlorosilane and chloro-dimethyl-vinyl silane, etc.
An anti-corrosive pigment can be incorporated in the radical
curable resin forming the intermediate layer with a view to giving
anti-corrosive property to the metal material. Further, various
types of pigments, fillers, dispersing agents, plasticizers and
other additives used for various purposes can be incorporated for a
plurality of objects including coloring and hiding effects. Ratios
of these substances in the composition vary over a wide range
according to the properties necessary for the intended final
product.
According to the process of the present invention, it is necessary
to use the radical curable resin in the absence of a solvent. The
presence of any of solvent is not allowed because of causing the
adhesive property to be lowered and preventing the surface from
being covered uniformly.
As for the film resin layer to be overlaid on the intermediate
layer comprising the radical curable resin, substances in the form
of a film comprising various types synthetic resins are used. Any
type of such resin can be used so long as it can provide
satisfaction for the properties required in accordance with the use
as a precoated metal. Most preferable are (1) acrylic film prepared
by melt extruding from a polymer composition containing at least 50
by weight percent of ester acrylate or ester methacrylate and by
applying other means, (2) a polyester film obtained by for example
melt extruding a polyester prepared from starting materials of a
polyethylene terepthalate or a polyester comprising of terephthalic
acid and ethylene glycol for the main components. (3) a vinyl
chloride resin film prepared by melt extruding from a vinyl
chloride resin consisting predominantly of vinyl chloride and by
applying other means, (4) a fluoropolymer resin film prepared by
melt extruding from a vinylidene fluoride resin consisting
predominantly of a vinylidene fluoride and by applying other means
and so forth. No any specific restrictions are made with respect of
means for forming the films as far as these films of the present
invention possess a property sufficient enough to meet the request
of the precoated metal.
In order for these films to form a surface layer of a laminated
construction and to give a variety of properties
(weather-proofness, surface hardness, anti-corrosiveness,
processability, decorativeness, etc), as the case may be, various
types of pigments, fillers, dispersing agents, plasticizers and
other additives for a plurality of purposes are incorporated.
In the present invention, specifically excellent results can be
brought forth in the case of using a resin forming the surface
layer and a resin forming the intermediate layer, each containing
the same monomer constituent. For example, if a polyester film is
used for the surface layer when an unsaturated polyester type resin
is used as the intermediate layer, a good result can be
achieved.
As for the method for forming a laminated structure, there are
various methods available and no specific restrictions are imposed
thereon. For example, it is possible to conduct in such a manner
that on the surface of the substrative metal material, the radical
curable solventless resin layer is formed by the customary film
forming means including by spraying, blushing, melt-coating,
electrodeposition process, etc. and by other various means,
followed by laminating a film as the surface layer thereon. It is
also possible to conduct in such a manner for example that the
radical curable non-solvent resin layer is formed at the back face
of the film forming the surface layer and thereafter, laid in
layers with the metal material.
According to the process of the present invention, by irradiating
the electron beam on the thus obtained laminated construction from
above the film, the radical curable resin layer is cured and
concurently the substrative material and the film are intimately
adhered to each other and unified. So far as the electron beam is
concerned, there are used any of the electron beams discharged from
various types electron beam accelerators such as cockcroft type
accelerator, cockcroft Walton type accelerator, Van de Graff type
accelerator, resonant transformer type accelerator, insulating core
transformer acclerator, linear accelerator type accelerator,
dynamitron type accelerator, high frequency type accelerator and
the like. Normally, the object of the present invention can be
achieved by giving a dose of 0.1- 20 Mrad, preferably 0.5-10 Mrad
with the electron beam having an acceleration energy of 0.1 to 3
MeV.
In the present invention, the total thickness of the film layer and
the radical curable resin layer is subjected to the restriction by
the maximum transmission distance of the electron beam. For
example, in the case of a material having a density of 1
g/cm.sup.3, the maximum transmission distance of the electron beam
having an energy of 3 MeV is 13.5 mm and consequently, the total
thickness should not exceed 13.5 mm. Now that the density and the
maximum transmission distance are in a relation of inverse
proportion, the total thickness will will be made thicker than 13.5
mm when the density is less than 1 g/cm.sup.3.
Each of the attached drawings FIG. 1 and FIG. 2 is a dose-depth
curve graph with a view of giving an explanation of the principle
of the present invention.
FIG. 1 shows a relation between the depth of a material having a
density of 1 g/cm.sup.3 in the case of the high energy electron
beam passing therethrough and the absorbed enery imparted by the
electron beam. According to this figure it is found out that the
absorbed energy on the surface of the material (depth = 0) is only
60 percent of the maximum absorbed energy. Namely, in the case of
the electron beam having an energy of 1.0 MeV, for example, the
maximum amount of absorption is indicated in the zone of 1.8 mm in
depth from the surface and the amount of absorption in the surface
zone is about 60 percent of the maximum.
FIG. 2 is a graph showing the generalization of FIG. 1 and it is
seen therein that the amount of energy absorption becomes maximum
in the zone of some depth from the surface.
Consequently, in the present invention, the maximum available
efficiency of energy and the improved cure speed can be obtained by
using this principle as long as the radical curable resin layer is
positioned in the zone of some depth showing the maximum amount of
absorption.
As well known, the radical curable resin is withheld from
conducting the curing reaction by oxygen in the air being a radical
inhibitor. According to the process of the present invention, the
film is laid on the upper layer thereby blocking the air and
achieving the effect of removing its radical prohibiting work.
Furthermore, in the present invention, in the case where the
intermediate layer contains a radical reactive monomer (for example
vinyl monomer such as styrene and methyl methacrylate), these
monomers can be effectively prevented from evaporation.
As for the process for the manufacture of the precoated metal it is
the hitherto used method that the laminated construction is formed
by causing acrylic film, vinyl chloride, resin film or
fluoropolymer to adhere by heat to the metal material in the
condition as they are or through the thermoadhesive layer. However,
in this case, a single-layer construction is formed by means of
adhesion of the independent film by pressure at the elevated
temperatures and hence, in general, intimate adhesiveness,
anti-corrosiveness, process ability are not sufficient. Almost all
of the films have a base of thermo-plastic resin formed into a film
by melt extrusion and consequently, the hardness is not
satisfactory.
With view of improving such deficient properties of the film it is
customarily conducted that the under-coating is generally, made to
the metal material thereby imparting it a role for contributing to
the intimate adhesion, anticorrosiveness or plural laminated film
is made by covering the film thereby imparting it the same role as
abovesaid. In the case of giving the undercoating to the metal
material, it is usual to dry and cure it at the elevated
temperatures after coating with the undercoating paint. If the
drying and curing are not sufficient, the remaining solvents or
substances originated from the curing are caused to swell from
their escape after the completion of covering the film and it give
rise to blister and causes the film to come off. The same thing
will be said in the case of coating the intermediate layer onto the
film. When the film or metal material is melt-coated with the
thermo-plastic intermediate layer, there are no problems as above
described. However, in this case, the intermediate layer is made
thermo-plastic whereby not a few deficiencies are seen in such
important properties as anti-corrosiveness, solvent-resistance
property and intimate adhesive property.
On the contrary, according to the present invention, the
intermediate layer is cured by irradating the electron beam to the
laminated construction whereby forming a cured resin having the
necessary properties and concurrently obtaining an adhesiveness
between the film and the substrative material. This is the effect
that has never been brought forth by the melt-adhesion process.
Further, it is another pronounced characteristic that by means of
the electron beam the film layer is cured, for instance, by
crosslinking, and in most cases, the deficient hardness of the film
layer consisting of thermo-plastic resin can be improved by
crosslinking.
The present invention will be explained in particulars by the
following Examples.
EXAMPLE 1
A film of 20.mu. in thickness was produced by melt extruding at
2500.degree. C a composition consisting of 70 parts of a copolymer
of methyl methacrylate-ethyl acrylate-methacrylic acid (the weight
ratio of 70/28/2), 15 parts of titanium oxide white, 7 parts of
phthalocyanine blue, 7 parts of chrome yellow and 0.2 part of
carbon black. (film.sub.I).
A composition consisting of methyl methacrylate-ethyl
acrylate-methacrylic acid(the weight ratio of 40/57/3) was
melt-extruded by 250.degree. C on the surface of the film 1 and
covered in the thickness of 5.mu. thereby producing a composite
film with a thickness of 25.mu.. (film II)
The below-described composition was coated in the thickness of
5.mu. on the surface of a zinc phosphate treated sheet steel (0.3
mm thick).
This composition is a liquid composition having a viscosity of 10
poise (3.degree.C) consisting of 70 parts by weight of a polymer
containing an unsaturated group at its side chain obtained by
reacting a copolymer of ethylacrylate-acrylic acid (85 parts/15
parts by weight) with 10 parts by weight of glycidyle methacrylate,
30 parts by weight of methyl methacrylate and 25 parts by weight of
zinc chromate.
After coating this composition in the thickness of 5.mu. as above
described, the film (I) was covered thereon and 3 Mrads of 0.5 MeV
electron beam was irradiated from above the film by means of the
Van de Graaff type accelerator. The obtained precoated sheet steel
was subjected to the various ASTM tests as shown in Table I.
Further, the film (II) was bonded at 1300.degree.C to the surface
of the zinc phosphate treated sheet steel (0.3 mm thick) with the
said covered layer downwardly whereby a laminated sheet steel was
made which was subjected to various similar tests.
TABLE 1
Precoated Metal by electron by film beam curing laminating method
method
__________________________________________________________________________
Pencil hardness (JIS G3312, NCCA No.11-12 3H F "Cross hatched"-tape
test (JIS G3312) 100/100 100/100 "Cross hatched"-Ericksen-
tape-test (6 mm) (JIS G3312) 100/100 70/100 180.degree.C bend (JIS
G3312) 0T (OK) 1T Impact test (1 kg .times. 50 cm) (JIS G3312) pass
pass Salt spray test (5% NaCl aqueous solution, 500 hus.) (JIS
Z2371) normal caused swelling
In the case of the precoated metal by means of the electron beam
curing method, the intermediate layer between the film and the
sheet steel is not only sufficiently cured during a short period of
time, but good physical properties as shown in Table I are obtained
because of an intimate adhesion between them. Further, in this case
it is worth attracting a special attention that the obtained
hardness is of such a sufficient degree that was not obtained by
the mere lamination of the thermoplastic acrylic films. It is
assumed that this is because the electron beam irradiation resulted
in cross-linking of the upper acrylic film. It is evident that by
the occurence of such cross-linkages the precoated metal is
concurrently given better resistances to solvent, stains and
chemicals.
EXAMPLE 2
A film with a thickness of 25.mu. was produced by melt extruding at
280.degree.C a composition consisting of 70 parts of polyethylene
terephthalate maleate (terephthalate/maleate = 7/3 mol ratio), 23
parts of titanium oxide white and 7 parts of phthalocyanine
blue.
0.3 mol of styrene was mixed with an unsaturated polyester produced
from 0.5 mol of phthalic acid, 0.3 mol of terephthalic acid, 0.2
mol of maleic acid and 1.1 mols of ethylene glycol. 100 parts of
this composition was combined with 7 parts of zinc chromate, 20
parts of iron oxide and 3.5 parts of zinc oxide thereby producing a
paint.
The above described paint was coated in the thickness of 5.mu. on
the surface of the zinc phosphate treated sheet steel and the said
polyester film was covered thereon and 4 Mrad of the 0.3 MeV
electron beam was irradiated. This caused the film and the sheet
steel to be unified whereby a precoated metal was obtained.
Its properties were such as shown in Table 2.
Table 2
Pencil Hardness 3H "Cross hatch"-Erickson- tape test (6 mm) 100/100
180.degree.C bend 11 Impact test (1 kg .times. 50 cm) pass Salt
spray test (5% NaCl aqueous solution, 500 hrs.) normal
EXAMPLE 3
A film with a thickness of 20.mu. was produced by melt-extruding a
composition consisting of 85 parts of polyvinyl chloride, 15 parts
of dioctyl phthalate, 15 parts of titanium oxide white and 7 parts
of phthalocyanine blue.
A polymer having a double bond at its side chain was produced by
reacting a copolymer consisting of 0.7 mol of vinyl chloride, 0.2
mol of ethyl acrylate and 0.1 mol of acrylic acid with 0.1 mol of
glycidyl methacrylate and a syrup consisting of 70 parts of this
polymer, 30 parts of methyl methacrylate, 17.5 parts of zinc
chromate, 8 parts of talc and 6.8 parts of zinc oxide was
produced.
The said syrup was coated on the zinc phosphate treated sheet steel
in the thickness of 5.mu. and the said film was covered thereon and
by giving it a dose of 4 Mrad radiation of the 0.3 MeV electron
beam, a precoated metal was produced. The obtained precoated metal
achieved good results in the adhesive property, weathering property
and anti-corrosive property.
The physical properties of the precoated metal are given in Table
3.
Table 3
Pencil hardness F "Cross hatch"-tape test 100/100 "Cross
hatch"-Ericksen (6mm)-tape test 100/100 180.degree. Bend 1T Impact
test (1 kg .times. 50 cm) pass Salt spray test (500 hrs)
excellent
Example 4
A zinc phosphate treated zinc sheet steel was coated in the
thickness of 3.mu. with an acrylic acid ester as a service coat and
cured. Thereafter, this metal material was coated in the thickness
of 5.mu. with the liquid composition of Example 3, followed by
covering it with the acrylic film I of Example 1 and by giving it a
dose of 4 Mrads radiation of 0.5 MeV electron beam by means of the
Van de Graaff, a precoated metal excellent in close adhesive
property was obtained.
The physical properties of the precoated metal are shown in Table
4.
Table
4 Pencil hardness H "Cross hatch"-tape test 100/100 180.degree.C
bend 1T Impact test (1 kg .times. 50 cm) pass Salt spray test (500
hrs.) excellent
Example 5
An aluminum sheet was coated in the thickness of 5.mu. with the
liquid composition of Example 3 and then covered with the acrylic
film of Example I, followed by giving it a dose of 4 Mrads
radiation of 0.5 MeV electron beam by means of the Van de Graaff,
whereby a precoated colored aluminum plate excellent in physical
properties including the close adhesive property was obtained.
The physical properties of the precoated plate are given in Table.
5.
Table 5
Pencil hardness 2H "Cross hatch"-Ericksen- tape test (6 mm) 100/100
180.degree.C bend 0T Impace test (1 kg .times. 40 cm) pass Salt
spray test (500 hrs.) normal Accelerated weathering (JIS Z0230)
weather-O-meter 1000 hrs. luster retaining ratio: more than 85%
Example 6
The following composition was coated in the thickness of 5.mu. on
the surface of the zinc phosphate treated sheet steel (0.3 mm
thick).
This composition is a liquid composition having a viscosity of 10
poises (23.degree.C) consisting of 70 parts by weight of a polymer
containing an unsaturated group at its side chain obtained by
reacting 100 parts by weight of a copolymer of methyl
methacrylate-butyl acrylate-glycidyl methacrylate (the weight ratio
of 30/55/15) with 15 parts by weight of methacrylic acid, 10 parts
by weight of methyl mechacrylate, 20 parts by weight of butyl
acrylate and 25 parts by weight of zinc chromate.
After coating this composition as above described, the
below-mentioned film was covered thereon and 5 Mrads of the 0.5 MeV
electron beam was irradiated by means of the Van de Graaff type
accelerator.
The said film is a film with a thickness of 20.mu. obtained by
shaping a polymer containing an unsaturated group at its side chain
obtained by reacting 100 parts by weight of a copolymer of methyl
methacrylate-butly acrylate-glycidyl methacrylate (the weight ratio
of 30/65/5) with 5 parts by weight of methacrylic acid and 50 parts
by weight, based on said polymer, of titanium oxide.
The physical properties of the obtained precoated sheet steel were
shown in Table 6.
Table 6
Pencil hardness H "Cross hatch"-tape test 100/100 "Cross
hatch"-Ericksen- tape test (6 mm) 100/100 180.degree.C bend 0T
Impact test (1 kg .times. 50 cm) pass Salt spray test (5% NaCl
aqueous solution, 500 hrs.) normal Accelerated weathering
weather-O-meter (JIS Z 0230) 600 hrs. reduction in luster: 5%
Example 7
The identical liquid composition as in Example 6 was coated in the
thickness of 6 .mu.on the iron phosphate treated sheet steel (0.18
mm thick) and the below-mentioned film was covered thereon and a
dose of 5 Mrads radiation of 0.3 MeV electron beam was
irradiated.
The said film is a film with a thickness of 20.mu. obtained in such
a manner that a xylene-butanol (the weight ratio of 1/1) solution
of a 8:2 (weight ratio) mixture of a polymer of methyl
methacrylate-ethyl acrylate-hydroxyethyl methacrylate-acrylic acid
(the weight ratio of 30/55/10/5) and hexamethoxymethylated melamine
was cast on a polypropylene plate and heated to be cured and
thereafter peeled off.
The physical properties of the obtained precoated sheet steel were
shown in Table 7.
Table 7
Pencil hardness 2H "Cross hatch"-Ericksen- tape test (6 mm) 100/100
180.degree. bend 2T Impact test (1 kg .times. 40 cm) pass Salt
spray test (5% NaCl aqueous solution, 500 hrs.) normal
Example 8
An unsaturated polyester was prepared from 0.3 mol of phthalic
acid, 0.6 mol of terephthalic acid, 0.1 mol of maleic acid and 1.1
mols of ethylene glycol and mixed with 0.1 mol of styrene. A paint
was produced by combining 100 parts of this composition with 6
parts of zinc chromate, 25 parts of iron oxide and 3.5 parts of
zinc oxide.
On the other hand, a film with a thickness of 20.mu. was obtained
by melt extruding at 280.degree.C a composition consisting of 70
parts of polyethylene terephthalate, 23 parts of titanium oxide
white and 7 parts of phthalocyanine blue.
The said paint was coated in the thickness of 7.mu. on the zinc
phosphate treated sheet steel and the said polyester film was
covered thereon and gave it a dose of 6 Mrads radiation of the 0.3
MeV electron beam whereby a precoated metal integrated with the
paint and sheet steel was obtained.
The physical properties of the precoated metal are given in Table
8.
Table 8
Pencil hardness 3H "Cross hatch"-tape test 100/100 180.degree. bend
1T Impact test (1 kg .times. 50 cm) pass Salt spray test (500 hrs.)
excellent
Example 9
A 30.beta. thick film was produced from a n-butanol-xylene solution
(having 30 parts by weight of TiO.sub.2 relating to the resin) of
70 parts by weight of alkyd resin consisting of 43 percent of
phthalic acid, 20 percent of glycerin and 36 percent of capric acid
and 30 parts by weight of n-butylated methylolated melamine.
A mixture of 20 parts of styrene and 80 parts of an unsaturated
polyester obtained through conducting the heat-condensation of 0.6
mol of phthalic acid, 0.3 mol of maleic acid, 0.1 mol of
methacrylic acid, 0.7 mol of glycerin and 0.3 mol of ethylene
glycol in the presence of 200 ppm of hydroquinone as a
polymerization inhibitor was coated on the surface of zinc
phosphate treated sheet steel (0.3 mm thick) in the thickness of
10.mu.. The said film was laid thereon and 5 Mrads of 0.5 MeV
electron beam was irradiated thereon by means of the Van de Graaff
type accelerator. The obtained precoated sheet steel was excellent
in adhesive property and in processability.
Table 9
Pencil hardness H "Cross hatch"-type test 100/100 180.degree. bend
2T Impact test (1 kg .times. 50 cm) pass Salt spray test (500 hrs.)
very good
Example 10
The condensation of 340 parts of trimethylol propane and 300 parts
of isophthalic acid was conducted by heating to 220.degree.C for 2
hours. The obtained polyester was cooled to 130.degree.C and added
thereto were 700 parts of partial hydrolyzed substances of phenyl
methyl dimethoxysilane, 3 parts of isopropyl titanate and 800 parts
of cellosolve acetate. The condensation was conducted by heating
for one hour. A paint was made by adding to the obtained solution
80 parts of TiO.sub.2 per 100 parts of the resin constituent in the
said solution and it was coated on the surface and heated to be
cured thereby obtaining a film.
0.2 mol of styrene was added to a polyester obtained by conducting
the condensation of 0.7 mol of isophthalic acid, 0.3 mol of maleic
acid, 0.6 mol of trimethylol propane and 0.2 mol of ethylene glycol
by heating to 130.degree.C. to 240.degree.C for 5 hours. The
resultant solution was coated in the thickness of 10.mu. on the
iron phosphate treated sheet steel and the said film was covered
thereon and by giving it a dose of 5 Mrads radiation of 0.3 MeV
electron beam, an unified precoated metal was obtained. This
material was good both in the adhesiveness of the covered layer and
processability.
The physical properties of the precoated metal are given in Table
10.
Table 10
Pencil hardness 2H "Cross hatch"-tape test 100/100) 180.degree.
bend 2T Impact test (1 kg .times. 50 cm) pass Salt spray test (500
hus.) excellent
Example 11
100 parts by weight of finely powdered polyvinyl chloride polymer a
molecular weight of 300,000, 20 parts by weight of dioctyl adipate,
50 parts by weight of bis-phenol A-epichlorohydrin type epoxy resin
(molecular weight:900, epoxy equivalent: 450), 8 parts by weight of
.beta.-napthylamine and 100 parts by weight of TiO.sub.2 were mixed
thereby obtaining a composition in the form of paste. This was
coated on the Teflon sheet in the form of film and heated thereby
obtaining a 45.mu. thick film.
80 mol percent of vinyl chloride, 10 mol percent of vinyl acetate
and 10 mol percent of acrylic acid were polymerized in methyl ethyl
ketone and thereafter, by adding thereto 10 mol percent of glycidyl
methacrylate the condensation was conducted by heating thereby
producing a solution of a polymer containing an unsaturated bond at
its side chain. This solution was admixed with 3 percent, based on
the resin in said solution, of zinc chromate. The resulting
solution was coated in the thickness of 10.mu. on the zinc
phosphate treated sheet steel and heated to 50.degree.C under
reduced pressure thereby removing the methyl ethyl ketone. The said
film was covered thereon and irradiated with a dose of 5 Mrads of
0.5 MeV electron beam by means of the Van de Graaff type
accelerator thereby causing the film, intermediate resin layer and
sheet steel to be unified and a precoated metal was obtained. The
properties of the resultant material were shown in Table 11 and it
exhibited good results both in processability and in adhesive
preperty.
Table 11
Pencil hardness H "Cross hatch"-tape test 100/100 108.degree. bend
1T Salt spray test No swelling (5% NaCl aqueous solution, normal in
all 40.degree.C, 200 hrs.) other respects
Example 12
100 parts of an aqueous dispersion containing 30 percent of a
vinylidene fluoride having a particle diameter of 1 to 20 .mu.and
100 parts of a tricresyl phosphate were mixed and this was
spray-coated on the chromium plated plate and treated by heating to
95.degree. to 180.degree.C for a total of 30 minutes. A film with a
thickness of 25.mu. was obtained.
A copolymer of 0.8 mol of methyl acrylate and 0.2 mol of acrylic
acid was admixed with 0.2 mol of glycidyl methacrylate and the
condensation was conducted by heating thereby producing a polymer
containing an unsaturated bond at its side chain.
A composition consisting of 100 parts by weight of this polymer, 20
parts by weight of methyl methacrylate and 50 parts by weight of
tricresyl phosphate was coated in the thickness of 10.mu. on the
zinc phosphate treated sheet steel and the said film was covered
thereon and given a dose of 5 Mrads radiation of 5 Mrads radiation
of 0.5 MeV electron beam by means of the Van de Graaff type
accelerator. The obtained precoated metal exhibited good adhesive
properties and passed the 1 kg .times. 30 cm. impact test by the Du
pont type impact testing apparatus.
Table 12
Pencil hardness H "Cross hatch"-tape test 100/100 180.degree. bend
1T Impact test (1 kg .times. 50 cm) pass Salt spray test (500 hrs.)
excellent
* * * * *